Manufacture of trisazoic coloring matters



Patented July 10, 1928.

warren Mam OSKAR KnE'cHr AND HANS isntirscrnor easier, SWITZERLAND,ASSIGIBTDRS To SOCIETY CHEMICAL WORKS roar/many sennoz, orgasm,s'wrrz'an-Limn MANUFACTURE or No Drawing. Application filed December 16,1924,

Up to the present 1-aryl-aminonaphthalene-sulfonic acids have beenspecially em-v ployed for the preparation of monoand disazo colors forW001. It has been discovered that when these 1-aryl-aminonaphthalenesulfonic acids are introduced as final components of trisazo colors;coloring matters for cotton are obtained which are extremely fast tolight and resistant to washing. These new coloring matters are preparedon the following principle. A diazotized derivative of the benzene ornaphthalene series is coupled with a diazotizable component; theintermediate product is diazotized again and is combined with the sameor another diazotiz'able component and then, after a furtherdiazotization, it is coupled with a l-aryl-aminonaphthalene sulfonicacid. Thesecolors are in accordance withthe formula g Benzene ornaphthalene derivative-120 M az"ol /l aao 1-- aryl a'mi'n'onaphthalenesulr'onic acid; where -M and M represent the residues of thediazotizable components such as l-naphthylamine, Cleves l-na'phthylaminesulfonic acid etc.

SOIaH N=N V zero commits MATTERS.

Serial 1%. 756,328, and in France January 11, 1924.

Example I.

Themonoazo color obtained by diaz'otizing 22.3 parts of Clevesl-naphthylamine sulfonic acid and coupling in acetic solution with 22.3parts of the same acid, is diazotized with the help of hydrochloric acidand of 6.9parts of sodium nitrite and is combined inacetic solution with22.3 parts of Cleves acid. The diazo color thus formed is isolated andthen is shaken, up with water, 6.9 parts of sodium nitrite are added andthe mixture is poured at a temperature of to C into an excess of dilutehydrochloric acid. When the diazotizationis finished; the diazoic isintroduced into a' solution of 321 parts er- 1phenyl-aminonaphthalene 8sullonate of sodium and the excess of mineral acid is neutralized bysodium acetate.

After agitation for several hours it is allowed to remain for l2 hoursat ordinary temperature', then heated and made alkaline withsodiumcarbonate, and thereupon salted out and filtered on. The dry coloris a grey black powder adapted as, dye cotton grey and is extremely fastto light and to washing.

The product obtained according ample has the followingformula:

SOsH

sulfonic acid are diazotized, then, with the addition of ice; a warmsolution at about to this eX- 45 C. of 18 parts of hydrochlorate ofanaphthylamine is poured into the diazoic solution. The free acid of thecolor is precipitated, filtered out and transformed into its sodiumsalt'by means of dilute caustic soda;

This is diazotized with sodium nitrite after the addition ofhydrochloric acid; the di azotized combination is filtered and then ismixed with a solution of 223 parts of Cleves acid and the free mineralacid is neutralized by an excess of sodium acetate. The disazoic coloris isolated and dissolved again and is Ewample IV.

By replacing the 18.7 parts of '1-methyl-2- aminobenzene l-sulfonic acidin Example IT The monoazo color, prepared according to Example I, isdiazotized as in that case; then the diazoic is mixed with 18 parts ofhydrochloride of a-naphthylamine and the excess of mineral acidneutralized by sodium acetate. The color precipitates in the form of itsfree acid, it is filtered and transformed into its sodium salt by dilutecaustic soda. It is diazotized in its turn and is coupled, in aceticsolution, with 32.1 parts of 1- phenyl-aminonaphthalene-8-sulfonate ofso dium. The color obtained from the solution madealkaline by sodiumcarbonate dyes cotton grey which is very fast to light'and to washing.

' Example V].

14.3 parts of a-llflPllllllYlElHllIlG are diazotized and coupled inacetic solution with 22.3 arts of Cleves l-naphthylamine sulfonic acid.WVhen the combination is complete, it is rendered alkaline with causticsoda and the sodium salt of the monoazo color is filtered out. This isthen diazotized by means of sodium nitrite and hydrochloric acid,

SOgH

diazotized by means of hydrochloric acid and i of sodium nitrite. Thediazoic compound is mixed with 32.1 parts of 1-phenyl-amino-'naphthalene-S-sulfonate of sodium, then the mass is heated, and afterhaving. been rendered alkaline with sodium carbonate, the color isprecipitated by common salt.

The color thus obtained'dyes cotton a bluish-grey which is very fast tolightiand to washing.

The product obtained according to this example has the followingformula:

mixed with asolution of 22.3 parts of Gleves 1-naphthylamine sulfonicacid and the mineral acid is neutralized by sodium acetate. The disazoiccolor, purified by filtration, is diazotized in the usual Way andcoupled at a temperature of about-5 C. with a solution of 32.1 parts ofl-phenyl-amino1iaphthalene-S-sulfonate of sodium; it is neutralizedimmediately by sodium acetate. When the combination is completed, it isheated and rendered slightly alkaline by sodium carbonate and the coloris precipitated by common salt. This product dyes cotton black, isextremely fast to light andto washing and very convenient for dischargeeffects.

Example VII.

The monoazo color obtained'by diazotizing 15 parts of p-aminoacetanilideand by com bining it in acetic solution with 22.3 parts of Gleves1"I'lflPhlll'lYlELlTllIIQTSUllEOIIlC acid, is filtered in the form ofits sodium salt. This salt is diazotized again by means of sodiumnitrite and hydrochloric acid and is coupled in acetic solution with22.3 parts of Cleves l-naphthylamine sulfonic acid. The disazoie coloris purified by filtering it and is diazotized by means of sodium nitriteand hydrochloric acid. and mixed with 32.1 parts of1-phenylaminonaphthalene-8-sulfonate of sodium as in Example VI.

The dry color is a grey blackpowder dyeing cotton from grey to black. Itis very fast to light and to Washing.

The product obtained according to this example has the followingformula:

CHa.CO

Ewample VIII. If the final component in Example I is replaced by thesame quantity of Cleves 1- phenyl-aminonaphthalene sulfonic acid, a

color is obtained which dyes cotton a greyish-blue which is very fast tolight and to washing.

WVhat we claim is:

1. A process for the manufacture of trisazoic coloring matters,consisting in coupling a diazo-derivative of the benzene and naphthaleneseries with a diazotizable component of the naphthylamine series, againdiazotizing the intermediate product thus obtained, combining the samewith a further diazotizable component of the naphthylamine series,rediazotizing again and finally coupling with a1-aryl-aminonap'hthalene-sulfonic acid.

2. As new articles of manufacture the herein described trisazoiccoloring matters, having the following general formula wherein R, standsfor a benzeneor naphthalene derivative, R for a hydrogen atom or thegroup SO Me, R for an aromatic radical and Me for an inorganic radical,these dyestuffs constituting grey-black powders suitable for dyeingcotton of grey to black tints extremely fast to light and washing.

In witness whereof we have hereunto signed our names this 4th day ofDecember, 1924.

OSKAR KNECHT. HANS .BRUTSGH.

